Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
  • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
  • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
  • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/42—Refining of petroleum waxes
  • C10G73/44—Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1022—Fischer-Tropsch products
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range

Definitions

• the present invention relates to a process to prepare a first middle distillates fraction, a second middle distillates fraction, and one or more base oils.
• Fischer-Tropsch derived middle distillates fractions typically have a high normal paraffin content (and low degree of isomerisation) .
• distillates fraction good cold flow properties, such as pour point or cloud point, are desired.
• WO 2009/080681 discloses a process to prepare a gas oil fraction and a residual base oil fraction, by
• a problem of the process disclosed in WO 2009/080681 is that although this process delivers a high amount of residual base oil, the overall gas oil yield is low.
• One of the above or other objects may be achieved according to the present invention by providing a process to prepare a first middle distillates fraction, a second middle distillates fraction, and one or more base oils, the process at least comprising the steps:
• step (b) separating the Fischer-Tropsch product stream of step (a) , thereby obtaining at least a low boiling fraction, boiling below a temperature in the range of from 300 to 450°C, and a high boiling fraction, boiling above a temperature in the range of from 300 to 450°C;
• step (c) subjecting the high boiling fraction of step (b) to a hydrocracking/hydroisomerization step to obtain an at least partially isomerised product stream;
• step (d) separating the product stream of step (c) , thereby obtaining a first middle distillates fraction and a residual fraction, wherein the residual fraction has a T10wt.% boiling point of between 200 and 450°C;
• step (e) dewaxing the low boiling fraction of step (b) to obtain a second middle distillates fraction
• step (d) dewaxing the residual fraction of step (d) to obtain one or more base oils.
• a low boiling fraction boiling below a temperature in the range of from 300 to 450°C at
• atmospheric conditions preferably comprises a C3 to C30 fraction, more preferably comprising a C3 to C23 fraction.
• a low boiling fraction comprises Fischer-Tropsch derived middle distillates range products.
• atmospheric residue range with a T5wt.% atmospheric boiling point in the range of from 300 and 450°C.
• the high boiling fraction boiling above 300 to 450°C at
• atmospheric conditions preferably comprises a C30 to C200 fraction, more preferably a C23 to C200 fraction, but may also contain C200+ molecules depending on the Fischer- Tropsch synthesis conditions.
• step (c) The preparation of the at least partially isomerised feedstock in step (c) has been described in e.g. WO
• step (d) the isomerised feedstock of step (c) is separated by means of distillation into a middle
• the middle distillates fraction may preferably be obtained via multiple distillation steps.
• step (d) the isomerised feedstock of step (c) is initially separated by means of distillation into a light fraction and a residual fraction.
• the light fraction may be obtained from the
• isomerised feedstock by distillation at atmospheric or at near atmospheric conditions.
• the residual fraction may be obtained from the isomerised feedstock by vacuum distillation.
• this vacuum distillation is performed at a pressure of between 1 and 250 mbar, more preferably between 10 and 100 mbar and most preferably between 10 and 75 mbar.
• the light fraction typically has a T95wt.% between 200 and 420 °C, more in particular between 300 and
• T95wt% is the temperature corresponding to the atmospheric boiling point at which a cumulative amount of 95% of the product is recovered.
• a gas chromatographic method such as ASTM D2887 can be used to determine the level of recovery.
• the light fraction comprises a first middle
• distillates fraction which middle distillates fraction may be separated by distillation. This may preferably be by atmospheric distillation or at slightly elevated pressure conditions.
• the first middle distillates fraction of step (d) preferably has a T10 wt . % boiling point from 150 to
• International Standard ISO 3015 is preferably below -15°C and more preferably below -20°C.
• the cold filter plugging point (CFFP) of the first middle distillates fraction of step (d) according to European Standard EN 116 is preferably below -10°C, more preferably below -15°C.
• the first middle distillates fraction may be further dewaxed to obtain a dewaxed first middle distillates fraction.
• Preferred dewaxing conditions are the same as those described below for step (e)
• the first middle distillates fraction comprises Fischer-Tropsch derived gas oil and Fischer-Tropsch derived kerosene.
• the residual fraction typically has a relatively low pour point according to ASTM D-5950 of below 40°C, more preferably below 35°C and even more preferably below 30°C.
• the residual fraction has a T10wt% boiling point of between 200 and 450 °C and preferably between 300 and
• step (e) the low boiling fraction of step (b) is dewaxed to obtain a second middle distillates fraction.
• dewaxing processes are catalytic dewaxing and solvent dewaxing.
• Catalytic and solvent dewaxing processes are known in the art and therefore not
• Dewaxing of the low boiling fraction in step (e) is preferably performed by means of a catalytic dewaxing process.
• Typical catalytic dewaxing processes are for example described in WO 2009/080681 and WO2012055755.
• catalytic dewaxing is performed in the presence of a catalyst comprising a molecular sieve and a group VIII metal.
• Suitable dewaxing catalyst are heterogeneous
• catalysts comprising molecular sieve, more suitably intermediate pore size zeolites and optionally in
• the intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm.
• the reference to ZSM-48 and EU-2 is used to indicate that all zeolites can be used that belong to the ZSM-48 family of disordered structures also referred to as the *MRE family and described in the Catalog of Disorder in Zeolite Frameworks published in
• any reference to ZSM-48 zeolite also is a reference to ZBM-30 and EU-11 zeolite.
• zeolites can be present in the catalyst composition especially if it is desired to modify its catalytic properties. It has been found that it can be advantageous to have present zeolite ZSM-12 which zeolite has been defined in the Database of Zeolite Structures published in 2007/2008 on behalf of the Structure Commission of the International Zeolite Assocation.
• Suitable Group VIII metals are nickel, cobalt, platinum and palladium.
• a Group VIII metal is platinum or palladium.
• the dewaxing catalyst suitably also comprises a binder.
• the binder can be non-acidic. Examples of
• the catalyst comprises a silica or titania binder.
• the second dewaxed middle distillates fraction has a cetane number according to ASTM D-613 greater than 70, suitably from 74 to 85.
• International Standard ISO 3015 is preferably below -40°C and more preferably below -50°C.
• the cold filter plugging point (CFFP) of the second middle dewaxed distillates fraction of step (e) according to European Standard EN 116 is preferably below -30°C, more preferably below -40°C.
• the second middle distillates fraction comprises Fischer-Tropsch derived gas oil and Fischer-Tropsch derived kerosene.
• C3 to C9 is separated from the second dewaxed middle distillates fraction by distillation, preferably at atmospheric conditions.
• a C3 to C9 fraction is meant a Fischer-Tropsch derived naphtha fraction .
• the present process suitably comprising a further step (h) wherein prior to performing step (e) , the first middle distillates
• fraction of step (d) or part of it is combined with the low boiling fraction of step (b) to obtain a mixture and wherein this mixture is dewaxed to obtain a third middle distillates fraction.
• the fraction of the first middle distillates that may be combined with the low boiling fraction of step (b) may cover 0-100%.
• the process of the present invention comprises a further step (i) , wherein the first middle distillates fraction of step (d) or part of it is combined with the second middle distillates fraction of step (e) to obtain a combined middle distillates product.
• the fraction of the first middle distillates that may be combined with the second middle distillates fraction of step (e) may cover 0-100%.
• the present invention provides a combined middle distillate product obtainable by the process according to the present invention.
• step (f) of the process according to the present invention the residual fraction of step (d) is dewaxed to obtain one or more base oils.
• Dewaxing of the residual fraction in step (f) is preferably performed by means of a catalytic dewaxing process.
• Typical catalytic dewaxing processes are for example described in WO 2009/080681 and WO2012055755.
• a dewaxed base oil is separated into further base oils by distillation.
• the present invention provides a light base oil grade obtainable by the process according to the present invention.
• the pour point of the light base oil grade according to ASTM D-5950 is below -5°C, preferably below -10°C, and more preferably below -15°C.
• the light base oil grade has a cloud point according to ASTM D-2500 of below -10°C, more preferably below -
• the present invention provides a heavy base oil grade obtainable by the process according to the present invention.
• a heavy base oil grade is meant further base oils having a kinematic viscosity at 100°C according to ASTM D-445 of from 10 to 40 mm 2 /s, preferably from 15 to 35 mm 2 /s, more preferably from 20 to 30 mm 2 /s, and most preferably 23 to 26 mm 2 /s.
• the pour point of the heavy base oil grade according to ASTM D-5950 is below 0°C, preferably below -20°C, more preferably below -40°C and most preferably below -50°C.
• step (d) between 20 to 70 wt . % of the residual fraction of step (d) is recycled to step (c) , more preferably between 30 to 60 wt . % and most preferably between 30 to 50 wt . % .
• the process scheme is generally referred to with reference numeral 1.
• a Fischer- Tropsch product stream is obtained (not shown) .
• This product is separated in a distillation column (not shown) into a fraction 10 boiling below a temperature in the range of from 300 to 450°C at atmospheric conditions and a fraction 20 boiling above a temperature in the range of from 300 to 450°C at atmospheric conditions.
• the high boiling fraction 20 is fed to a hydrocracking/hydroisomerization reactor 3 wherein part of the components boiling above a temperature in the range of from 300 to 450°C are converted to product boiling below a temperature in the range of from 300 to 450°C.
• the residual fraction 40 is fed to a catalytic dewaxing reactor 5 to obtain a base oil 70.
• the effluent 70 of reactor 5 is distilled in 6 to recover in one or more distillation steps one or more distillate base oils that can be grouped into light grade base oils 80, having a kinematic viscosity at at 100°C between 2 and 10 mm 2 /s and heavy grade base oils 90, having a kinematic viscosity at 100°C between 10 and 40 mm 2 /s.
• part of the residual fraction 40A is recycled to reactor 3 by combining 40A with the high boiling fraction 20.
• the low boiling fraction 10 is fed to a catalytic dewaxing reactor 7 wherein the low boiling fraction is converted to a second dewaxed middle distillates fraction 100.
• the middle distillates fraction 100 is distilled in distillation column 8 to recover a gas oil 110 and kerosene 120.
• part of first middle distillates fraction 30A is fed to catalytic dewaxing reactor 7.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

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• 2013
  • 2013-06-28 EP EP13734030.3A patent/EP2867344A1/de not_active Withdrawn
  • 2013-06-28 CA CA2877182A patent/CA2877182A1/en not_active Abandoned
  • 2013-06-28 WO PCT/EP2013/063734 patent/WO2014001550A1/en active Application Filing
  • 2013-06-28 US US14/408,579 patent/US20150203769A1/en not_active Abandoned
  • 2013-06-28 RU RU2015102627A patent/RU2015102627A/ru not_active Application Discontinuation

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